Carboxamide Compound and Use of the Same

ABSTRACT

A carboxamide compound represented by the formula (I): 
     
       
         
         
             
             
         
       
     
     [wherein Q represents a nitrogen-containing 6-membered aromatic heterocyclic group optionally fused with a benzene ring, two or more ring constitutional atoms of the heterocyclic group are a nitrogen atom, and the heterocyclic group may be substituted with at least one group selected from the group consisting of a C1-C3 alkyl group etc.], and a plant disease controlling agent comprising this as an active ingredient.

TECHNICAL FIELD

The present invention relates to a carboxamide compound, and use of thesame.

BACKGROUND ART

Development of a plant disease controlling agent has been progressed,and compounds having controlling activity on many plant diseases havebeen found out.

However, plant disease controlling activity of these compounds is notsufficient in some cases.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a compound havingexcellent plant disease controlling activity.

The present invention is as follows:

[1] A carboxamide compound (hereinafter, referred to as presentcompound) represented by the formula (I):

[wherein Q represents a nitrogen-containing 6-membered aromaticheterocyclic group optionally fused with a benzene ring, two or more ofring constitutional atoms of the heterocyclic group are nitrogen atoms,the heterocyclic group may be substituted with at least one groupselected from the group consisting of a C1-C3 alkyl group, a C1-C3haloalkyl group, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group anda nitro group,R¹ represents a C1-C3 alkyl group or a C2-C5 alkoxyalkyl group, R²represents a hydrogen atom or a C1-C3 alkyl group, or R¹ and R² arebound to each other at an end to represent a C3-C4 alkylene group, andR³ represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group].

[2] The carboxamide compound according to [1], wherein Q represents anitrogen-containing 6-membered aromatic heterocyclic group optionallyfused with a benzene ring, two or more of ring constitutional atoms ofthe heterocyclic group are nitrogen atoms, the heterocyclic group may besubstituted with at least one group selected from of the groupconsisting of a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3alkoxy group, a halogen atom, a cyano group and a nitro group,

R¹ represents a C1-C3 alkyl group or a C2-C5 alkoxyalkyl group, R²represents a hydrogen atom or a C1-C3 alkyl group, or R¹ and R² arebound to each other at an end, to represent a C3-C4 alkylene group, andR³ represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group.

[3] The carboxamide compound according to [1], wherein Q is a 6-memberedaromatic heterocyclic group in which two or more of ring constitutionalatoms are nitrogen atoms, and the heterocyclic group may be substitutedwith at least one group selected from the group consisting of a C1-C3alkyl group, C1-C3 haloalkyl group, a C1-C3 alkoxy group, a C1-C3alkylthio group, a (C1-C3 alkoxycarbonyl)C1-C3 alkylthio group, ahalogen atom, a cyano group and a nitro group.

[4] The carboxamide compound according to [1], wherein Q is a 6-memberedaromatic heterocyclic group in which two or more of ring constitutionalatoms are nitrogen atoms, and the heterocyclic group may be substitutedwith at least one group selected from the group constituting of a C1-C3alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, a halogenatom, a cyano group and a nitro group.

[5] The carboxamide compound according to [1], wherein Q is aheterocyclic group which is a 2-pyrimidinyl group, a 4-pyrimidinylgroup, a 5-pyrimidinyl group, a 2-pyrazinyl group, a 3-pyridazinylgroup, a 4-pyridazinyl group, a 1,2,4-triazin-3-yl group, a1,3,5-triazin-2-yl group, a quinoxalin-2-yl group, a quinazolin-2-ylgroup or a cinnolin-3-yl group, and the heterocyclic group may besubstituted with at least one group selected from the group consistingof a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, aC1-C3 alkylthio group, a (C1-C3 alkoxycarbonyl) C1-C3 alkylthio group, ahalogen atom, a cyano group and a nitro group.

[6] The carboxamide compound according to [1], wherein Q is aheterocyclic group which is a 2-pyrimidinyl group, a 4-pyrimidinylgroup, a 5-pyrimidinyl group, a 2-pyrazinyl group, a 3-pyridazinylgroup, a 4-pyridazinyl group, a 1,2,4-triazin-3-yl group, a1,3,5-triazin-2-yl group, a quinoxalin-2-yl group, a quinazolin-2-ylgroup or a cinnolin-3-yl group, and the heterocyclic group may besubstituted with at least one group selected from the group consistingof a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, ahalogen atom, a cyano group and a nitro group.

[7] The carboxamide compound according to [1], wherein Q is aheterocyclic group which is a 2-pyrimidinyl group, a 4-pyrimidinylgroup, a 5-pyrimidinyl group, a 2-pyrazinyl group, a 3-pyridazinylgroup, a 4-pyridazinyl group, a 1,2,4-triazin-3-yl group or a1,3,5-triazin-2-yl group, and the heterocyclic group may be substitutedwith at least one group selected from the group consisting of a C1-C3alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, a C1-C3alkylthio group, a (C1-C3 alkoxycarbonyl)C1-C3 alkylthio group, ahalogen atom, a cyano group and a nitro group.

[8] The carboxamide compound according to [1], wherein Q is aheterocyclic group which is a 2-pyrimidinyl group, a 4-pyrimidinylgroup, a 5-pyrimidinyl group, a 2-pyrazinyl group, a 3-pyridazinylgroup, a 4-pyridazinyl group, a 1,2,4-triazin-3-yl group and a1,3,5-triazin-2-yl group, and the heterocyclic group may be substitutedwith at least one group selected from the group consisting of a C1-C3alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, a halogenatom, a cyano group and a nitro group.

[9] The carboxamide compound according to any one of [1] to [8], whereinR³ is a hydrogen atom or a C1-C3 alkyl group.

[10] The carboxamide compound according to any one of [1] to [8],wherein R³ is a hydrogen atom or a halogen atom.

[11] A plant disease controlling agent, comprising a carboxamidecompound as defined in any one of [1] to [10] as an active ingredient,and an inert carrier.

[12] A method of controlling a plant disease, comprising a step oftreating a plant or a soil where a plant grows with an effective amountof the carboxamide compound as defined in any one of [1] to [10].

[13] Use of a carboxamide compound as defined in any one of [1] to [10]for controlling a plant disease.

Examples of the C1-C3 alkyl group represented by R¹ include a methylgroup, an ethyl group, a propyl group and an isopropyl group, andexamples of the C2-C5 alkoxyalkyl group include a methoxymethyl group,an ethoxymethyl group, and a propoxymethyl group.

Examples of the C1-C3 alkyl group represented by R² include a methylgroup, an ethyl group, a propyl group and an isopropyl group.

Examples of the C3-C4 alkylene group in which R¹ and R² are bound toeach other at an end include a trimethylene group and a tetramethylenegroup.

Examples of the halogen atom represented by R³ include a fluorine atom,a chlorine atom, a bromine atom and an iodine atom.

Examples of the C1-C3 alkyl group represented by R³ include a methylgroup, an ethyl group, a propyl group, and an isopropyl group.

Q represents a nitrogen-containing 6-membered aromatic heterocyclicgroup optionally fused with a benzene ring, two or more of ringconstitutional atoms of the heterocyclic group are nitrogen atoms, andthe heterocyclic group may be substituted with at least one groupselected from the group consisting of a C1-C3 alkyl group, a C1-C3haloalkyl group, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group anda nitro group.

Examples of such the heterocyclic group include a 2-pyrimidinyl group, a4-pyrimidinyl group, a 5-pyrimidinyl group, a 2-pyrazinyl group, a3-pyridazinyl group, a 4-pyridazinyl group, a 1,2,4-triazin-3-yl group,a 1,3,5-triazin-2-yl group, a quinazolin-2-yl group in which apyrimidine ring is fused with a benzene ring, a quinoxalin-2-yl group inwhich a pyrazinyl ring is fused with a benzene ring, a cinnolin-3-ylgroup in which a pyridazine ring is fused with a benzene ring, andgroups in which these heterocyclic groups are substituted with at leastone group selected from the group consisting of a C1-C3 alkyl group(e.g. methyl group, ethyl group, propyl group etc.), a C1-C3 haloalkylgroup (e.g. trifluoromethyl group, etc.), a C1-C3 alkoxy group (e.g.methoxy group, ethoxy group etc.), a C1-C3 alkylthio group (e.g.methylthio group, ethylthio group and propylthio group), a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group (e.g. methoxycarbonylmethylthiogroup, ethoxycarbonylmethylthio group and 1-(methoxycarbonyl)ethylthiogroup), a halogen atom (e.g. fluorine atom, chlorine atom etc.), a cyanogroup and a nitro group.

Specific examples of the heterocyclic group represented by Q include:

a 2-pyrimidinyl group, a 4-pyrimidinyl group, a 5-pyrimidinyl group, a2-pyrazinyl group, a 3-pyridazinyl group, a 4-pyridazinyl group, a1,2,4-triazin-3-yl group, a 1,3,5-triazin-2-yl group, a5-chloro-2-pyrimidinyl group, a 2-chloro-5-pyrimidinyl group, a5-chloro-2-pyrazinyl group, a 6-chloro-3-pyridazinyl group, a5-methyl-2-pyrimidinyl group, a 2-methyl-5-pyrimidinyl group, a5-methyl-2-pyrazinyl group, a 6-methyl-3-pyridazinyl group, a5-trifluoromethyl-2-pyrimidinyl group, a 2-methoxy-5-pyrimidinyl group,a 5-cyano-2-pyrazinyl group, a 6-nitro-3-pyridazinyl group, aquinoxalin-2-yl group, a quinazolin-2-yl group, a cinnolin-3-yl group, a6-chloro-2-pyrazinyl group, a 6-methoxy-4-pyrimidinyl group, a4-methyl-2-pyrimidinyl group, a 6-methoxy-3-pyridazinyl group, a6-bromo-3-pyridazinyl group, a 6-cyano-3-pyridazinyl group, a6-methylthio-3-pyridazinyl group, a6-methoxycarbonylmethylthio-3-pyridazinyl group, a 5-bromo-2-pyrimidinylgroup, a 6-ethyl-3-pyridazinyl group, a 6-propyl-3-pyridazinyl group, a2-ethoxy-5-pyrimidinyl group, a 6-ethoxy-3-pyridazinyl group, a6-ethylthio-3-pyridazinyl group, a6-ethoxycarbonylmethylthio-3-pyridazinyl group, a 5-fluoro-2-pyrimidinylgroup, a 2-fluoro-5-pyrimidinyl group, a 5-fluoro-2-pyrazinyl group, a6-fluoro-3-pyridazinyl group, a 2-bromo-5-pyrimidinyl group, a5-bromo-2-pyrazinyl group, a 5-cyano-2-pyrimidinyl group and a2-cyano-5-pyrimidinyl group.

Examples of embodiments of the present compound include the followingcarboxamide compounds in the present compounds.

A carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 5-pyrimidinyl group, a2-pyrazinyl group, a 3-pyridazinyl group, a 4-pyridazinyl group, a1,2,4-triazin-3-yl group, a 1,3,5-triazin-2-yl group, a quinoxalin-2-ylgroup, a quinazolin-2-yl group or a cinnolin-3-yl group, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group anda nitro group in the formula (I);

a carboxamide compound in which Q is a 6-membered aromatic heterocyclicgroup having two or more nitrogen atoms as ring constitutional atoms,and the heterocyclic group may be substituted with at least one groupselected from the group consisting of a C1-C3 alkyl group, a C1-C3haloalkyl group, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group anda nitro group in the formula (I);a carboxamide compound in which Q is a 6-membered aromatic heterocyclicgroup having two or more nitrogen atoms as ring constitutional atoms,and the heterocyclic group may be substituted with at least one groupselected from the group consisting of a C1-C3 alkyl group, a C1-C3haloalkyl group, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group anda nitro group, and R³ is a hydrogen atom or a C1-C3 alkyl group in theformula (I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 5-pyrimidinyl group, a2-pyrazinyl group, a 3-pyridazinyl group, a 4-pyridazinyl group, a1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-yl group, the heterocyclicgroup may be substituted with at least one group selected from the groupconsisting of a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3alkoxy group, a C1-C3 alkylthio group, a (C1-C3 alkoxycarbonyl)C1-C3alkylthio group, a halogen atom, a cyano group and a nitro group, and R³is a hydrogen atom or a C1-C3 alkyl group in the formula (I);a carboxamide compound in which Q is a heterocyclic group which is apyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a1,2,4-triazinyl group or a 1,3,5-triazinyl group, and the heterocyclicgroup may be substituted with at least one group selected from the groupconsisting of a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3alkoxy group, a C1-C3 alkylthio group, a (C1-C3 alkoxycarbonyl)C1-C3alkylthio group, a halogen atom, a cyano group and a nitro group in theformula (I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 5-pyrimidinyl group, a2-pyrazinyl group, a 3-pyridazinyl group, a 4-pyridazinyl group, a1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-yl group, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group anda nitro group in the formula (I);a carboxamide compound in which Q is a heterocyclic group which is apyrimidinyl group, a pyrazinyl group and a pyridazinyl group, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group anda nitro group in the formula (I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 2-pyrazinyl group, a3-pyridazinyl group, a 1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-ylgroup, and the heterocyclic group may be substituted with at least onegroup selected from the group consisting of a C1-C3 alkyl group, a C1-C3haloalkyl group, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group anda nitro group in the formula (I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 5-pyrimidinyl group, a2-pyrazinyl group, a 3-pyridazinyl group, a 4-pyridazinyl group, a1,2,4-triazin-3-yl group, a 1,3,5-triazin-2-yl group, a quinoxalin-2-ylgroup, a quinazolin-2-yl group or a cinnolin-3-yl group, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a halogen atom, a cyano group and a nitrogroup in the formula (I);a carboxamide compound in which Q is a 6-membered aromatic heterocyclicgroup having two or more nitrogen atoms as ring constitutional atoms,and the heterocyclic group may be substituted with at least one groupselected from the group consisting of a C1-C3 alkyl group, a C1-C3haloalkyl group, a C1-C3 alkoxy group, a halogen atom, a cyano group anda nitro group in the formula (I);a carboxamide compound in which R³ is a hydrogen atom or a C1-C3 alkylgroup in the formula (I);a carboxamide compound in which Q is a 6-membered aromatic heterocyclicgroup having two or more nitrogen atoms as ring constitutional atoms,the heterocyclic group may be substituted with at least one groupselected from the group consisting of a C1-C3 alkyl group, a C1-C3haloalkyl group, a C1-C3 alkoxy group, a halogen atom, a cyano group anda nitro group, and R³ is a hydrogen atom or a C1-C3 alkyl group in theformula (I);

a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 5-pyrimidinyl group, a2-pyrazinyl group, a 3-pyridazinyl group, a 4-pyridazinyl group, a1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-yl group, the heterocyclicgroup may be substituted with at least one group selected from the groupconsisting of a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3alkoxy group, a halogen atom, a cyano group and a nitro group, and R³ isa hydrogen atom or a C1-C3 alkyl group in the formula (I);

a carboxamide compound in which Q is a heterocyclic group which is apyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a1,2,4-triazinyl group or a 1,3,5-triazinyl group, and the heterocyclicgroup may be substituted with at least one group selected from the groupconsisting of a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3alkoxy group, a halogen atom, a cyano group and a nitro group in theformula (I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 5-pyrimidinyl group, a2-pyrazinyl group, a 3-pyridazinyl group, a 4-pyridazinyl group, a1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-yl group, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a halogen atom, a cyano group and a nitrogroup in the formula (I);a carboxamide compound in which Q is a heterocyclic group which is apyrimidinyl group, a pyrazinyl group or a pyridazinyl group, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a halogen atom, a cyano group and a nitrogroup in the formula (I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 2-pyrazinyl group, a3-pyridazinyl group, a 1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-ylgroup, and the heterocyclic group may be substituted with at least onegroup selected from the group consisting of a C1-C3 alkyl group, a C1-C3haloalkyl group, a C1-C3 alkoxy group, a halogen atom, a cyano group anda nitro group in the formula (I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 2-pyrazinyl group, a3-pyridazinyl group, a 1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-ylgroup, and the heterocyclic group may be substituted with at least onegroup selected from the group consisting of a methyl group, a methoxygroup, a methylthio group, a methoxycarbonylmethylthio group, a bromineatom, a chlorine atom and a cyano group in the formula (I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 2-pyrazinyl group, a3-pyridazinyl group, a 1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-ylgroup, and the heterocyclic group may be substituted with at least onegroup selected from the group consisting of a methyl group, a methoxygroup, a chlorine atom, and a cyano group in the formula (I);a carboxamide compound in which R² is a hydrogen atom, and R³ is ahydrogen atom in the formula (I);a carboxamide compound in which R² is a methyl group, and R³ is ahydrogen atom in the formula (I);a carboxamide compound in which R² is a hydrogen atom, and R³ is amethyl group in the formula (I);a carboxamide compound in which R¹ is a methyl group, R² is a hydrogenatom, and R³ is a hydrogen atom in the formula (I);a carboxamide compound in which R¹ is a methyl group, R² is a methylgroup, and R³ is a hydrogen atom in the formula (I);a carboxamide compound in which R¹ is a methyl group R² is a hydrogenatom, and R³ is a methyl group in the formula (I);a carboxamide compound in which R² is a hydrogen atom, and R³ is afluorine atom in the formula (I);a carboxamide compound in which R² is a methyl group, and R³ is afluorine atom in the formula (I);a carboxamide compound in which R² is a hydrogen atom, and R³ is achlorine atom in the formula (I);a carboxamide compound in which R² is a methyl group, and R³ is achlorine atom in the formula (I);a carboxamide compound in which R¹ is a methyl group, R² is a hydrogenatom, and R³ is a fluorine atom in the formula (I);a carboxamide compound in which R¹ is a methyl group, R² is a methylgroup, and R³ is a fluorine atom in the formula (I);a carboxamide compound in which R¹ is a methyl group, R² is a hydrogenatom, and R³ is a chlorine atom in the formula (I);a carboxamide compound in which R¹ is a methyl group, R² is a methylgroup, and R³ is a chlorine atom in the formula (I);a carboxamide compound in which R¹ and R² are bound to each other at anend to be a trimethylene group, and R³ is a hydrogen atom in the formula(I);a carboxamide compound in which R¹ and R² are bound to each other at anend to be a trimethylene group, and R³ is a fluorine atom in the formula(I);a carboxamide compound in which R¹ and R² are bound to each other at anend to be a trimethylene group, and R³ is a chlorine atom in the formula(I);a carboxamide compound in which Q is a heterocyclic group which is apyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a1,2,4-triazinyl group or a 1,3,5-triaziyl group, the heterocyclic groupmay be substituted with at least one group selected from the groupconsisting of a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3alkylthio group, a halogen atom, a cyano group and anitro group, R¹ is a C1-C3 alkyl group, R² is a hydrogen atom or a C1-C3alkyl group, and R³ is a hydrogen atom or a C1-C3 alkyl group in theformula (I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 5-pyrimidinyl group, a2-pyrazinyl group, a 3-pyridazinyl group, a 4-pyridazinyl group, a1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-yl group, the heterocyclicgroup may be substituted with at least one group selected from the groupconsisting of a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3alkoxy group, a C1-C3 alkylthio group, a (C1-C3 alkoxycarbonyl)C1-C3alkylthio group, a halogen atom, a cyano group, and a nitro group, R¹ isa C1-C3 alkyl group, R² is a hydrogen atom or a C1-C3 alkyl group, andR³ is a hydrogen atom or a C1-C3 alkyl group in the formula (I);a carboxamide compound in which Q is a heterocyclic group which is apyrimidinyl group, a pyrazinyl group or a pyridazinyl group, theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a C1-C3 alkyl group, a C1-C3 haloalkoxygroup, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group, anda nitro group, R¹ is a C1-C3 alkyl group, R² is a hydrogen atom or aC1-C3 alkyl group, and R³ is a hydrogen atom or a C1-C3 alkyl group inthe formula (I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 2-pyrazinyl group, a3-pyridazinyl group, a 1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-ylgroup, the heterocyclic group may be substituted with at least one groupselected from the group consisting of a C1-C3 alkyl group, a C1-C3haloalkyl group, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl) C1-C3 alkylthio group, a halogen atom, a cyano group anda nitro group, R¹ is a C1-C3 alkyl group, R² is a hydrogen atom or aC1-C3 alkyl group, and R³ is a hydrogen atom or a C1-C3 alkyl group inthe formula (I);a carboxamide compound in which Q is a heterocyclic group which is apyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a1,2,4-triazinyl group or a 1,3,5-triazinyl group, the heterocyclic groupmay be substituted with at least one group selected from the groupconsisting of a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3alkoxy group, a halogen atom, a cyano group and a nitro group, R¹ is aC1-C3 alkyl group, R² is a hydrogen atom or a C1-C3 alkyl group, and R³is a hydrogen atom or a C1-C3 alkyl group in the formula (I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 5-pyrimidinyl group, a2-pyrazinyl group, a 3-pyridazinyl group, a 4-pyridazinyl group, a1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-yl group, the heterocyclicgroup may be substituted with at least one group selected from the groupconsisting of a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3alkoxy group, a halogen atom, a cyano group and a nitro group, R¹ is aC1-C3 alkyl group, R² is a hydrogen atom or a C1-C3 alkyl group, and R³is a hydrogen atom or a C1-C3 alkyl group in the formula (I);a carboxamide compound in which Q is a heterocyclic group which is apyrimidinyl group, a pyrazinyl group or a pyridazinyl group, theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a halogen atom, a cyano group and a nitrogroup, R¹ is a C1-C3 alkyl group, R² is a hydrogen atom or a C1-C3 alkylgroup, and R³ is a hydrogen atom or a C1-C3 alkyl group in the formula(I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 2-pyrazinyl group, a3-pyridazinyl group, a 1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-ylgroup, the heterocyclic group may be substituted with at least one groupselected from the group consisting of a C1-C3 alkyl group, a C1-C3haloalkyl group, a C1-C3 alkoxy group, a halogen atom, a cyano group anda nitro group, R¹ is a C1-C3 alkyl group, R² is a hydrogen atom or aC1-C3 alkyl group, and R³ is a hydrogen atom or a C1-C3 alkyl group inthe formula (I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 2-pyrazinyl group, a3-pyridazinyl group, a 1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-ylgroup, the heterocyclic group may be substituted with at least one groupselected from the group consisting of a methyl group, a methoxy group, amethylthio group, a methoxycarbonylmethylthio group, a bromine atom, achlorine atom and a cyano group, R¹ is a C1-C3 alkyl group, R² is ahydrogen atom or a C1-C3 alkyl group, and R³ is a hydrogen atom or aC1-C3 alkyl group in the formula (I);a carboxamide compound in which Q is a heterocyclic group which is a2-pyrimidinyl group, a 4-pyrimidinyl group, a 2-pyrazinyl group, a3-pyridazinyl group, a 1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-ylgroup, the heterocyclic group may be substituted with at least one groupselected from the group consisting of a methyl group, a methoxy group, achlorine atom and a cyano group, R¹ is a C1-C3 alkyl group, R² is ahydrogen atom or a C1-C3 alkyl group, and R³ is a hydrogen atom or aC1-C3 alkyl group in the formula (I);a carboxamide compound represented by the formula (I-100):

in which R¹ represents a C1-C3 alkyl group or a C2-C5 alkoxyalkyl group,R² represents a hydrogen atom or a C1-C3 alkyl group,R³ represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group,R¹⁰⁰ represents a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group or anitro group;a carboxamide compound in which R¹ is a C1-C3 alkyl group or a C2-C5alkoxyalkyl group,R² is a hydrogen atom or a C1-C3 alkyl group,R³ is a hydrogen atom, a halogen atom or a C1-C3 alkyl group, andR¹⁰⁰ is a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, aC1-C3 alkoxy group, a halogen atom, a cyano group or a nitro group inthe formula (I-100);a carboxamide compound represented by the formula (I-101):

in which R¹ represents a C1-C3 alkyl group or a C2-C5 alkoxyalkyl group,R² represents a hydrogen atom or a C1-C3 alkyl group,R³ represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group,R¹⁰¹ represents a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group or anitro group;a carboxamide compound in which R¹ is a C1-C3 alkyl group or a C2-C5alkoxyalkyl group,R² is a hydrogen atom or a C1-C3 alkyl group,R³ is a hydrogen atom, a halogen atom or a C1-C3 alkyl group, andR¹⁰¹ is a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, aC1-C3 alkoxy group, a halogen atom, a cyano group or a nitro group inthe formula (I-101);a carboxamide compound represented by the formula (I-102):

in which R¹ represents a C1-C3 alkyl group or a C2-C5 alkoxyalkyl group,R² represents a hydrogen atom or a C1-C3 alkyl group,R³ represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group,R¹⁰² represents a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group or anitro group;a carboxamide compound in which R¹ is a C1-C3 alkyl group or a C2-C5alkoxyalkyl group,R² is a hydrogen atom or a C1-C3 alkyl group,R³ is a hydrogen atom, a halogen atom or a C1-C3 alkyl group, andR¹⁰² is a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, aC1-C3 alkoxy group, a halogen atom, a cyano group or a nitro group inthe formula (I-102);a carboxamide compound represented by the formula (I-103):

in which R¹ represents a C1-C3 alkyl group or a C2-C5 alkoxyalkyl group,R² represents a hydrogen atom or a C1-C3 alkyl group,R³ represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group,R¹⁰³ represents a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group or anitro group;a carboxamide compound in which R¹ is a C1-C3 alkyl group or a C2-C5alkoxyalkyl group,R² is a hydrogen atom or a C1-C3 alkyl group,

R³ is a hydrogen atom, a halogen atom or a C1-C3 alkyl group, and

R¹⁰³ is a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, aC1-C3 alkoxy group, a halogen atom, a cyano group or a nitro group inthe formula (I-103);a carboxamide compound represented by the formula (I-104):

in which R¹ represents a C1-C3 alkyl group or a C2-C5 alkoxyalkyl group,R² represents a hydrogen atom or a C1-C3 alkyl group,R³ represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group,R¹⁰⁴ represents a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group or anitro group;a carboxamide compound in which R¹ is a C1-C3 alkyl group or a C2-C5alkoxyalkyl group,R² is a hydrogen atom or a C1-C3 alkyl group,R³ is a hydrogen atom, a halogen atom or a C1-C3 alkyl group, andR¹⁰⁴ is a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, aC1-C3 alkoxy group, a halogen atom, a cyano group or a nitro group inthe formula (I-104);a carboxamide compound represented by the formula (I-105):

in which R¹ represents a C1-C3 alkyl group or a C2-C5 alkoxyalkyl group,R² represents a hydrogen atom or a C1-C3 alkyl group,R³ represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group,R¹⁰⁵ represents a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group or anitro group;a carboxamide compound in which R¹ is a C1-C3 alkyl group or a C2-C5alkoxyalkyl group,R² is a hydrogen atom or a C1-C3 alkyl group,R³ is a hydrogen atom, a halogen atom or a C1-C3 alkyl group, andR¹⁰⁵ is a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, aC1-C3 alkoxy group, a halogen atom, a cyano group or a nitro group inthe formula (I-105);a carboxamide compound represented by the formula (I-106):

in which R¹ represents a C1-C3 alkyl group or a C2-C5 alkoxyalkyl group,R² represents a hydrogen atom or a C1-C3 alkyl group,R³ represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group,R¹⁰⁶ represents a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group or anitro group;a carboxamide compound in which R¹ is a C1-C3 alkyl group or a C2-C5alkoxyalkyl group,R² is a hydrogen atom or a C1-C3 alkyl group,R³ is a hydrogen atom, a halogen atom or a C1-C3 alkyl group, andR¹⁰⁶ is a hydrogen atom, a C1-C3 alkyl group, a C1-C3 haloalkyl group, aC1-C3 alkoxy group, a halogen atom, a cyano group or a nitro group inthe formula (I-106),

Next, a process for preparing the present compound will be explained.The present compound can be prepared, for example, according to thefollowing (Process A), (Process B) and (Process C).

In the (Process A), (Process B), (Process C), and Reference Process, ifnecessary, a protecting group for protecting a particular functionalgroup may be used, and the protecting group can be deprotected under thesuitable condition.

(Process A)

The present compound can be prepared by reacting a compound representedby the formula (II) and a compound represented by the formula (III).

[wherein Q represents a nitrogen-containing 6-membered aromaticheterocyclic group optionally fused with a benzene ring, two or more ofring constitutional atoms of the heterocyclic group are nitrogen atoms,the heterocyclic group may be substituted with at least one groupselected from the group consisting of a C1-C3 alkyl group, a C1-C3haloalkyl group, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl) C1-C3 alkylthio group, a halogen atom, a cyano group anda nitro group,R¹ represents a C1-C3 alkyl group or a C2-C5 alkoxyalkyl group, R²represents a hydrogen atom or a C1-C3 alkyl group, or R¹ and R² arebound to each other at an end, to represent a C3-C4 alkylene group,R³ represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group,andR⁴ represents a C1-C10 alkyl group]

The reaction is performed usually in the presence of a solvent. Ifnecessary, the reaction may be performed while a C1-C10 alcohol producedaccompanying with progression of the reaction is removed by adsorbsion,distillation, or azeotropy or the like.

Examples of the solvent to be used in the reaction include halogenatedaromatic hydrocarbons such as chlorobenzene, bromobenzene and the like,aromatic hydrocarbons such as toluene, xylene, and the like, acid amidessuch as N,N-dimethylformamide and the like, and a mixture thereof.

At the reaction, the compound represented by the formula (II) is usuallyused at a ratio of 0.1 to 5 moles per 1 mole of the compound representedby the formula (III).

A reaction temperature in the reaction is usually in a range of 80 to180° C., and a reaction time is usually in a range of 0.1 to 24 hours.After completion of the reaction, the present compound represented bythe formula (I) can be isolated, for example, by performing thefollowing post-treatment procedure.

The reaction mixture is cooled to room temperature, the resultant solidis collected by filtration, and the solid is washed with an organicsolvent, and dried; the reaction mixture is concentrated under reducedpressure, and the resulting solid is further washed with an organicsolvent, and dried.

The isolated present compound represented by the formula (I) may befurther purified by a procedure such as chromatography,recrystallization and the like.

(Process B)

The present compound can be prepared by reacting a compound representedby the formula (XIII) and a compound represented by the formula (III)using carbonyldiimidazole.

[wherein R¹, R², R³ and Q are as defined above.]

The reaction is performed usually in the presence of a solvent. Examplesof the solvent to be used in the reaction include nitrites such asacetonitrile, propionitrile and the like, ethers such as diethyl ether,t-butyl methyl ether, tetrahydrofuran, 1,4-dioxane and the like,aromatic hydrocarbons such as toluene, xylene, and the like, acid amidessuch as N,N-dimethylformamide and the like, and a mixture thereof.

At the reaction, the compound represented by the formula (III) is usedusually at a ratio of 0.1 to 5 moles per 1 mole of the compoundrepresented by the formula (XIII). Carbonyldiimidazole is used usuallyat a ratio of 0.1 to 5 moles per 1 mole of the compound represented bythe formula (XIII).

A reaction temperature in the reaction is usually in a range of −10 to150° C. and a reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the present compound represented bythe formula (I) can be isolated by performing a post-treatment proceduresuch as the resulting solid being collected by filtration, washing thesolid with an organic solvent, drying and so on. The isolated presentcompound represented by the formula (I) may be further purified by aprocedure such as chromatography, recrystallization and the like.

(Process C)

The present compound can be prepared by reacting a compound representedby the formula (XIII) and a compound represented by the formula (XV) inthe presence of alkaline earth metal triflate such as magnesiumtriflate, calcium triflate and the like.

[wherein R¹, R², R³ and Q are as defined above]

The reaction is performed usually in the presence of a solvent. Examplesof the solvent used in the reaction include aromatic hydrocarbons suchas toluene, xylene and the like.

At the reaction, the compound represented by the formula (XV) is usuallyused at a ratio of 1 mole per 1 mole of the compound represented by theformula (XIII), and the alkaline earth metal triflate is usually used ata ratio of 0.01 to 0.1 mole per 1 mole of the compound represented bythe formula (XIII).

A reaction temperature in the reaction is usually in a range of 100 to150° C. and a reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the present compound represented bythe formula (I) can be isolated by performing a post-treatment proceduresuch as the reaction mixture being cooled, the resulting solid beingcollected by filtration, washing the solid with an organic solvent,drying and so on. The isolated compound represented by the formula (I)may be further purified by a procedure such as chromatography,recrystallization and the like. The compound represented by the formula(XV) can be prepared from a compound represented by the formula (XVI):

OCN-Q  (XVI)

and 3,5-dimethylimidazole.

Next, a process for preparing an intermediate for preparing the presentcompound will be explained as Reference Process.

(Reference Process 1)

A compound represented by the formula (II-1) among the compoundsrepresented by the formula (II) can be prepared, for example, from acompound represented by the formula (IV) according to the followingscheme.

[wherein Q is as defined, R¹¹ represents a C1-C3 alkyl group or a C2-C5alkoxyalkyl group, R²¹ represents a hydrogen atom or a C1-C3 alkylgroup, R³¹ represents a hydrogen atom or a C1-C3 alkyl group, and R⁴represents a C1-C10 alkyl group]

Step (1-1)

A compound represented by the formula (V-1) can be prepared by reactinga compound represented by the formula (IV) with an azide compound (e.g.sodium azide, and trimethylsilyl azide), and further reacting theresulting product and an alcohol compound (e.g. methanol, and ethanol).

The reaction is performed usually in the presence of a solvent. Examplesof the solvent used in the reaction include halogenated hydrocarbonssuch as carbon tetrachloride and the like, halogenated aromatichydrocarbons such as chlorobenzene, bromobenzene and the like, aromatichydrocarbons such as toluene, xylene and the like, acid amides such asN,N-dimethylformamide and the like and a mixture thereof.

At the reaction, the azide compound is used usually at a ratio of 1 to 5moles per 1 mole of the compound represented by the formula (IV), andthe alcohol compound is used usually at a ratio of 1 mole per 1 mole ofthe azide compound.

When the compound represented by the formula (IV) is reacted with theazide compound, a reaction temperature is usually in a range of −20 to100° C., and a reaction time is usually in a range of 0.1 to 24 hours.When the resulting product is reacted with the alcohol compound, areaction temperature is usually in a range of −20 to 10° C., and areaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound represented by theformula (V-1) can be isolated by performing a post-treatment proceduresuch as the solid produced in the reaction mixture being collected byfiltration, washing the solid with an organic solvent, drying and so on.The isolated compound represented by the formula (V-1) can be furtherpurified by a procedure such as chromatography, recrystallization andthe like. Alternatively, the compound represented by the formula (V-1)can be also prepared by the method shown in Tetrahedron Letters No. 4,pp. 243-246, 1976.

Step (1-2)

A compound represented by the formula (VI-1) can be prepared by reactinga compound represented by the formula (V-1) with a compound representedby the formula (X):

R¹¹—X  (X)

[wherein R¹¹ is as defined above, and X represents a leaving group suchas a halogen atom (e.g. chlorine atom, bromine atom and iodine atom), asulfonyloxy group (e.g. methanesulfonyloxy group, methoxysulfonyloxygroup, and p-toluenesulfonyloxy group) and the like] in the present of abase.

The reaction is usually performed in the presence of a solvent. Examplesof the solvent used in the reaction include ketones such as acetone,ethyl methyl ketone and the like, halogenated aromatic hydrocarbons suchas chlorobenzene, bromobenzene and the like, aromatic hydrocarbons suchas toluene, xylene and the like, acid amides such asN,N-dimethylformamide and the like, ethers such as tetrahydrofuran,1,4-dioxane and the like, nitrites such as acetonitrile and the like,and a mixture thereof.

Examples of the compound represented by the formula (X) which is used inthe reaction include methyl iodide, methyl bromide, dimethyl sulfate,ethyl iodide, propyl iodide, and chloromethyl ethyl ether.

Examples of the base used in the reaction include carbonates such aspotassium carbonate, cesium carbonate and the like and alkali metalhydrides such as sodium hydride, potassium hydride and the like.

At the reaction, the compound represented by the formula (X) is usedusually at a ratio of 1 to 5 moles per 1 mole of the compoundrepresented by the formula (VI-1), and the base is usually used at aratio of 1 to 5 mole per 1 mole of the compound represented by theformula (VI-1).

A reaction temperature in the reaction is usually in a range of −20 to150° C., and a reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound represented by theformula (VI-1) can be isolated by performing the followingpost-treatment procedure.

The reaction mixture is cooled to room temperature, and filtered, thefiltrate is concentrated under reduced pressure, and the resulting solidis washed with an organic solvent, and dried;

Water is added to the reaction mixture, this is extracted with anorganic solvent, and the organic layer is concentrated.

The isolated compound represented by the formula (VI-1) may be furtherpurified by a procedure such as chromatography, recrystallization andthe like.

Step (1-3)

A compound represented by the formula (II-1) can be prepared by reactinga compound represented by the formula (VI-1) with dialkyl malonaterepresented by the formula:

CH₂(COOR⁴)₂

(wherein R⁴ is as defined above)in the presence of a base.

The reaction is usually performed in the presence of a solvent. Examplesof the solvent used in the reaction include ethers such astetrahydrofuran, 1,4-dioxane and the like, halogenated aromatichydrocarbons such as chlorobenzene, bromobenzene and the like, aromatichydrocarbons such as toluene, xylene and the like, acid amides such asN,N-dimethylformamide and the like, and a mixture thereof.

Examples of the dialkyl malonate represented by the formula CH₂(COOR⁴)₂used in the reaction include dimethyl malonate, and diethyl malonate.

Examples of the base used in reaction include:

metal alkoxides represented by the formula:

NaOR⁴

(wherein R⁴ is as defined above), and alkali metal hydrides such assodium hydride, potassium hydride and the like.

At the reaction, the dialkyl malonate is used usually at a ratio of 1 to5 moles per 1 mole of the compound represented by the formula (VI-1),and the base is used usually at a ratio of 1 to 5 moles per 1 mole ofthe compound represented by the formula (VI-1).

A temperature in the reaction is usually in a range of −10 to 150° C.,and a reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound represented by theformula (II-1) can be isolated by performing a post-treatment procedure,such as the reaction mixture being cooled to room temperature, addingacidic water such as dilute hydrochloric acid and the like to thereaction mixture to make the aqueous layer acidic, extracting this withan organic solvent, drying and concentrating the organic layer, and soon. The isolated compound represented by the formula (II-1) may befurther purified by a procedure such as chromatography,recrystallization and the like.

In addition, a compound represented by the formula (II-2) among thecompound represented by the formula (II) can be prepared, for example,according to the following scheme.

[wherein Q, R¹¹ and R⁴ are as defined above, R²² represents a C1-C3alkyl group, R³² represents a halogen atom, and R⁴ represents a C1-C10alkyl group]

Step (1′-1)

A compound represented by the formula (V-2) can be prepared according tothe method described in Tetrahedron Letters No. 4, pp 243-246, 1976.

A step (1′-2) and a step (1′-3) are performed as in the step (1-2) andthe step (1-3).

(Reference Process 2)

The compound represented by the formula (II) can be also preparedaccording to the following scheme.

[wherein R¹, R², R³, R⁴ and Q are as defined above]

Step (2-1)

The compound represented by the formula (II) can be prepared by reactinga compound represented by the formula (VII) with a compound representedby the formula (VIII).

The reaction can be performed usually in the absence of a solvent.Alternatively, the reaction may be performed in the presence of asolvent while an alcohol compound produced accompanying a reaction isremoved by azeotropy and the like. Examples of the solvent used in thereaction include halogenated aromatic hydrocarbons such aschlorobenzene, bromobenzene and the like, aromatic hydrocarbons such astoluene, xylene and the like, acid amides such as N,N-dimethylformamideand the like, and a mixture thereof.

At the reaction, the compound represented by the formula (VIII) is usedusually at a ratio of 1 to 50 moles per 1 mole of the compoundrepresented by the formula (VII).

A reaction temperature in the reaction is usually in a range of 100 to250° C., and a reaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the compound represented by theformula (II) can be isolated, for example, by performing the followingpost-treatment procedure.

The reaction mixture is cooled to room temperature, the resulting solidis filtered, and the solid is washed with an organic solvent, and dried;

After the reaction mixture is cooled to room temperature, water is addedto the reaction mixture, this is extracted with an organic solvent, andthe organic layer is concentrated.

The isolated compound represented by the formula (II) may be furtherpurified by a procedure such as chromatography, recrystallization andthe like.

(Reference Process 3)

Among the compound represented by the formula (XIII), a compoundrepresented by the formula (XIII-1) can be prepared from a compoundrepresented by the formula (XVII) according to the following scheme.

[wherein R¹³ represents a C1-C3 alkyl group]

(Step 3-1)

A compound represented by the formula (XVIII) can be prepared byreacting a compound represented by the formula (XVII) with diketenerepresented by the formula (XIX) in the presence of tertiary amine orpyridines (first stage), and reacting the resulting product with acompound represented by the formula (XX) (second stage).

Each reaction is usually performed in the presence of a solvent.Examples of the solvent used in the reaction include nitrites such asacetonitrile, propionitrile and the like, ethers such as diethyl ether,t-butyl methyl ether, tetrahydrofuran, 1,4-dioxane and the like,halogenated aromatic hydrocarbons such as chlorobenzene, bromobenzeneand the like, aromatic hydrocarbons such as toluene, xylene and thelike, and a mixture thereof.

In the reaction at the first stage, diketene represented by the formula(XIX) is used usually at a ratio of 1 mole per 1 mole of the compoundrepresented by the formula (XVII).

In the reaction at the first stage, examples of the tertiary amine usedinclude triethylamine and tri-n-propylamine; examples of pyridinesinclude pyridine and 4-dimethylaminopyridine. In the reaction at thefirst stage, tertiary amine or pyridines is used usually at a ratio of 1mole per 1 mole of the compound represented by the formula (XVII).

A reaction temperature at the first stage is usually in a range of 0 to40° C., and a reaction time is usually in a range of 0.1 to 24 hours.

The reaction mixture obtained by the reaction at the first stage isusually used as it is in the reaction at the second stage.

The reaction at the second stage is usually performed by mixing areaction mixture obtained at the first stage and a compound representedby the formula (XX).

In the reaction at the second stage, the compound represented by theformula (XX) is usually used at a ratio of 2 mole per 1 mole of thecompound represented by the formula (XVII).

A reaction temperature in the reaction at the second stage is usually ina range of 0 to 40° C., and a reaction time is usually in a range of 0.1to 24 hours.

After completion of the reaction at the second stage, the compoundrepresented by the formula (XVIII) can be isolated by performing apost-treatment procedure, such as by adding an acid (e.g. dilutehydrochloric acid, dilute sulfuric acid) to the reaction mixture, andcollecting the resultant crystal by filtration, drying and so on. Theisolated compound represented by the formula (XVIII) may be furtherpurified by a procedure such as chromatography, recrystallization andthe like.

(Step 3-2)

A compound represented by the formula (XIII-1) can be prepared byretaining a compound represented by the formula (XVIII) at 40 to 120° C.for 0.1 to 24 hours.

The procedure is usually performed in the presence of a solvent.Examples of the solvent used in the procedure include nitrites such asacetonitrile, propionitrile and the like, ethers such as t-butyl methylether, tetrahydrofuran, 1,4-dioxane and the like, halogenated aromatichydrocarbons such as chlorobenzene, bromobenzene and the like, aromatichydrocarbons such as toluene, xylene and the like, and a mixturethereof.

After disappearance of the compound represented by the formula (XVIII)is confirmed by an analysis means such as thin layer chromatography andthe like, the compound represented by the formula (XIII-1) can beisolated by performing a post-treatment procedure, such as addition ofthe resulting mixture to water, extraction this with an organic solvent,concentration of an organic layer and the like. The isolated compoundrepresented by the formula (XIII-1) may be further purified by aprocedure such as chromatography, recrystallization and the like.

(Reference Process 4)

Among a compound represented by the formula (XIII), a compoundrepresented by the formula (XIII-2) can be prepared by reacting acompound represented by the formula (XVIII) with a halogenating agent at−10 to 30° C. (first stage) and retaining the resulting product at 40 to120° C. for 0.1 to 24 hours (second stage).

[wherein R³⁴ represents a halogen atom, and R¹³ is as defined above]

The reaction at the first stage is usually performed in the presence ofa solvent. Examples of the solvent used in the reaction include nitritessuch as acetonitrile, propionitrile and the like, ethers such as diethylether, t-butyl methyl ether, tetrahydrofuran, 1,4-dioxane and the like,halogenated aromatic hydrocarbons such as chlorobenzene, bromobenzeneand the like, aromatic hydrocarbons such as toluene, xylene and thelike, and a mixture thereof.

Examples of the halogenating agent used in the reaction at the firststage include N-fluoropyridinium salt such asN,N′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate) and the like, andN-halogenosuccinimides such as N-chlorosuccinimide, N-bromosuccinimide,N-iodosuccinimide and the like.

At the reaction, the halogenating agent is usually used at a ratio of0.5 to 2 moles per 1 mole of the compound represented by the formula(XVIII).

A reaction temperature in the reaction at the first stage is usually ina range of −10 to 30° C. and a reaction time is usually in a range of0.1 to 5 hours.

The reaction mixture obtained in the reaction at the first stage can beusually used as it is in a procedure at the second stage.

The procedure at the second stage is performed usually by retaining thereaction mixture obtained in the first stage at 40 to 120° C.

Thereafter, the compound represented by the formula (XIII-2) can beisolated by performing a post-treatment procedure, such as by adding thereaction mixture to water, extracting with an organic solvent,concentration of the organic layer and the like. The isolated compoundrepresented by the formula (XIII-2) may be further purified by aprocedure such as chromatography, recrystallization and the like.

The compound represented by the formula (III) is commercially availableor can be synthesized by the known methods (e.g. methods described inIndian Journal of Chemistry, Section B: Organic Chemistry IncludingMedicinal Chemistry (1998), 37B(1), 84p, Bioorganic & MedicinalChemistry Letters (2002), 12(16), 2221-2224p, JP-B No. 52-009736,Journal of Organic Chemistry (1994), 59(24), 7299-7305p, Phosphorus,Sulfur and Silicon and the Related Elements (2002), 177(11), 2651-2659p,Bioorganic & Medicinal Chemistry (2001), 9(12), 3231-3241, ChemischeBerichte (1960), 93, 2190-2097p, “The Chemistry of HeterocyclicCompounds (John Wiley & Sons, Inc.)”).

The compounds represented by the formula (IV), the compounds representedby the formula (VII), the compounds represented by the formula (VIII),the compounds represented by the formula (X) and dialkyl malonate arecommercially available or can be synthesized using the known methods.

Examples of a plant disease which can be controlled by the presentcompound include the following diseases:

Pyricularia oryzae and Cochliobolus miyabeanus and Rhizoctonia solani ofrice;Erysiphe graminis, Gibberella zeae, Fusarium graminearum, Fusariumculmorum, F. avenaceum, Microdochium nivale, Puccinia striiformis, P.graminis, P. recondita, P. hordei, Typhula sp., Micronectriella nivalis,Ustilago tritici, U. nuda, Tilletia caries, Pseudocercosporellaherpotrichoides, Rhynchosporium secalis, Septoria tritici, Leptosphaerianodorum and Gaeumanomyces graminis, of wheat and barley; Diaporthecitri, Elsinoe fawcetti, Penicillium digitatum and P. italicum ofcitrus; Sclerotinia mali, Valsa mali, Podosphaera leucotricha,Alternaria mali and Venturia inaequalis of apple; Venturia nashicola, V.pirina, Alternaria kikuchiana and Gymnosporangium haraeanum of pear;Sclerotinia cinerea, Cladosporium carpophilum and Phomopsis sp. ofpeach; Elsinoe ampelina, Glomerella cingulata, Uncinula necator,Phakopsora ampelopsidis, Guignardia bidwellii and Plasmopara viticola,of grape; Gloeosporium kaki, Cercospora kaki and Mycosphaerella nawae ofJapanese persimmon;Colletotrichum lagenarium, Sphaerotheca fuliginea, Mycosphaerellamelonis, Fusarium oxysporum, Pseudoperonospora cubensis, Phytophthorasp. and Pythium sp. of gourd;Alternaria solani, Cladosporium fulvum and Phytophthora infestans oftomato;Phomopsis vexans and Erysiphe cichoracearum, of eggplant; Alternariajaponica and Cercosporella brassicae of Cruciferae vegetables;Puccinia allii of leek; Cercospora kikuchii, Elsinoe glycines, Diaporthephaseolorum var. sojae and Phakospora pachrhizii of soybean;Colletotrichum lindemthianum of kidney bean; Cercospora personata andCercospora arachidicola of peanut; Erysiphe pisi of pea; Alternariasolani and Phytophthora infestans of potato; Sphaerotheca humuli ofstrawberry; Exobasidium reticulatum and Elsinoe leucospila of tea;Alternaria longipes, Erysiphe cichoracearum, Colletotrichum tabacum,Peronospora tabacina and Phytophthora nicotianae of tobacco; Cercosporabeticola of sugar beet; Diplocarpon rosae and Sphaerotheca pannosa ofrose; Septoria chrysanthemi-indici and Puccinia horiana ofchrysanthemum; Botrytis cinerea and Sclerotinia sclerotiorum of variouscrops; Sclerotinia homeocarpaa and Rhizoctonia solani of lawn.

The plant disease controlling agent of the present invention may be thepresent compound itself, but usually, the agent contains the presentcompound, and an inert carrier such as a solid carrier, a liquid carrierand the like, and is formulated in preparations by further mixing asurfactant, and other adjuvant for preparations. Examples of such thepreparations includes emulsifiable concentrates, wettable powders, waterdispersible granule, emulsion preparations, flowable preparations,dusts, and granules. These preparations contain the present compound asan active ingredient usually at 0.1 to 90% in terms of ratio by weight.

Examples of the solid carrier used upon formulating the preparationsinclude fine powders and particles of minerals such as kaolin clay,attapulgite clay, bentonite, montmorillonite, acid clay, pyrophyllite,talc, diatomaceous earth, calcite and the like, natural organics such ascorncob powders, walnut shell flour and the like, synthetic organicssuch as urea and the like, salts such as calcium carbonate, ammoniumsulfate and the like, synthetic inorganic substances such as synthetichydrous silicon oxide and the like, and the examples of the liquidcarrier include aromatic hydrocarbons such as xylene, alkylbenzene,methylnaphthalene and the like, alcohols such as 2-propanol, ethyleneglycol, propylene glycol, ethylene glycol monomethyl ether and the like,ketones such as acetone, cyclohexanone, isophorone and the like,vegetable oils such as soybean oil, cottonseed oil and the like,aliphatic hydrocarbons, esters, dimethyl sulfoxide, acetonitrile, andwater.

Examples of the surfactant includes anionic surfactants such asalkylsulfate ester salt, alkylarylsulfonate salt, dialkylsulfosuccinatesalt, polyoxyethylene alkyl aryl ether phosphate ester salt,ligninsulfonate salt, naphathalene sulfonate formaldehyde polycondensateand the like, and noinic surfactants such as polyoxyethylene alkyl arylether, polyoxyethylene alkyl polyoxypropylene block copolymer, sorbitanfatty acid ester and the like.

Examples of other adjuvant for preparations include water-solublepolymers such as polyvinyl alcohol, polyvinylpyrrolidone and the like,polysaccarides such as gum arabic, alginic acid and a salt thereof, CMC(carboxymethylcellulose), xanthan gum and the like, inorganic substancessuch as aluminum magnesium silicate, alumina sol and the like,preservative, coloring agent, and stabilizers such as PAP (acidicisopropyl phosphate), BHT and the like.

The plant disease controlling agent of the present invention is used,for example, for protecting a plant against a plant disease by foliagetreatment of the plant, or is used for protecting a plant growing on asoil against a plant disease by treating the soil. When the plantdisease controlling agent of the present invention is used byfoliage-treating a plant, or when the agent is used by treating a soil,the amount of treatment varies depending on a kind of a crop which is aplant to be controlled, a kind of a disease to be controlled, aninfestation level of a disease to be controlled, a preparation form, atreating term, weather condition and the like, and the amount in termsof the present compound per 10000 m² is usually 1 to 5000 g, preferably5 to 1000 g.

In the case of emulsifiable concentrates, wettable powders, flowablepreparations and the like, a plant is usually treated by diluting theagent with water, followed by spraying. A concentration of the presentcompound is usually in a range of 0.0001 to 3% by weight, preferably ina range of 0.0005 to 1% by weight. In the case of dusts, granules andthe like, a plant is treated with the agent without dilution.

Alternatively, the plant disease controlling agent of the presentinvention may be used by a treating method such as seed disinfection.Examples of the method of disinfecting a seed include a method ofimmersing a plant seed in a plant disease controlling agent of thepresent invention which has been prepared so that a concentration of thepresent compound is adjusted to 1 to 1000 ppm, a method of spraying orapplying the plant disease controlling agent of the present inventionhaving a concentration of the present compound 1 to 1000 ppm on plantseeds, and a method of coating plant seeds with the plant diseasecontrolling agent of the present invention which has been formulatedinto powders.

The plant disease controlling method of the present invention is usuallyperformed by treating a plant which is expected to develop a disease ora soil where the plant grows, and/or treating a plant which is confirmedto have developed a disease or a soil where the plant grows with aneffective amount of the plant disease controlling agent of the presentinvention.

The plant disease controlling agent of the present invention is usuallyused as a plant disease controlling agent for horticulture, i.e., aplant disease controlling agent for controlling a plant disease inplowed field, paddy, orchard, tea garden, meadow, lawn and so on.

The plant disease controlling agent of the present invention may be used(mixed or combined) in conjunction with other fungicides, insecticides,acaricides, nematicides, herbicides, plant growth controlling agentsand/or fertilizers.

Examples of an active ingredient of such other fungicides includechlorothalonil, fluazinam, dichlofluanid, fosetyl-Al, cyclic imidoderivatives (captan, captafol, folpet etc.), dithiocarbamate derivatives(maneb, mancozeb, thiram, ziram, zineb, propineb etc.), inorganic ororganic copper derivatives (basic copper sulfate, copper oxychloride,copper hydroxide, oxine copper etc.), acylalanine derivatives(metalaxyl, furalaxyl, ofurace, cyprofuram, benalaxyl, oxadixyl etc.),strobilurin compounds (kresoxim-methyl, azoxystrobin, trifloxystrobin,picoxystrobin, pyraclostrobin, dimoxystrobin, fluoxastrobin,metominostrobin etc.), anilinopyrimidine derivatives (cyprodinil,pyrimethanil, mepanipyrim etc.), phenylpyrrole derivatives (fenpiclonil,fludioxonil etc.), imide derivatives (procymidone, iprodione,vincrozolin etc.), benzimidazole derivatives (carbendazim, benomyl,thiabendazol, thiophanate-methyl etc.), amine derivatives(fenpropimorph, tridemorph, fenpropidin, spiroxamine etc.), azolederivatives (propiconazole, triadimenol, prochloraz, penconazole,tebuconazole, flusilazole, diniconazole, bromuconazole, epoxiconazole,difenoconazole, cyproconazole, metconazole, triflumizole, tetraconazole,myclobutanil, fenbuconazole, hexaconazole, fluquinconazole,triticonazole, bitertanol, imazalil, flutriafol etc.), cymoxanil,dimethomorph, famoxadone, fenamidone, iprovalicarb, benthiavalicarb,cyazofamid, picobenzamid, mandipropamide, zoxamide, ethaboxam, boscalid,pyribencarb, fluopicolide, fenhexamid, quinoxyfen, proquinazid,diethofencarb, acibenzolar-S-methyl, guazatine and penthiopyrad.

Examples of the present compound include the following compounds.

Carboxamide compounds represented by the following formulas (i) to(xxviii):

In the formulas (i) to (xxviii), Q is any of the following groups.

A 2-pyrimidinyl group, a 4-pyrimidinyl group, a 5-pyrimidinyl group, a2-pyrazinyl group, a 3-pyridazinyl group, a 4-pyridazinyl group, a1,2,4-triazin-3-yl group, a 1,3,5-triazin-2-yl group, a5-chloro-2-pyrimidinyl group, a 2-chloro-5-pyrimidinyl group, a5-chloro-2-pyrazinyl group, a 6-chloro-3-pyridazinyl group, a5-methyl-2-pyrimidinyl group, a 2-methyl-5-pyrimidinyl group, a5-methyl-2-pyrazinyl group, a 6-methyl-3-pyridazinyl group, a5-trifluoromethyl-2-pyrimidinyl group, a 2-methoxy-5-pyrimidinyl group,a 5-cyano-2-pyrazinyl group, a 6-nitro-3-pyridazinyl group, aquinoxalin-2-yl group, a quinazolin-2-yl group, a cinnolin-3-yl group, a6-chloro-2-pyrazinyl group, a 6-methoxy-4-pyrimidinyl group, a4-methyl-2-pyrimidinyl group, a 6-methoxy-3-pyridazinyl group, a6-bromo-3-pyridazinyl group, a 6-cyano-3-pyridazinyl group, a6-methylthio-3-pyridazinyl group, a6-methoxycarbonylmethylthio-3-pyridazinyl group, a 5-bromo-2-pyrimidinylgroup, a 6-ethyl-3-pyridazinyl group, a 6-propyl-3-pyridazinyl group, a2-ethoxy-5-pyrimidinyl group, a 6-ethoxy-3-pyridazinyl group, a6-ethylthio-3-pyridazinyl group, a6-ethoxycarbonylmethylthio-3-pyridazinyl group, a 5-fluoro-2-pyrimidinylgroup, a 2-fluoro-5-pyrimidinyl group, a 5-fluoro-2-pyrazinyl group, a6-fluoro-3-pyridazinyl group, a 2-bromo-5-pyrimidinyl group, a5-bromo-2-pyrazinyl group, a 5-cyano-2-pyrimidinyl group and a2-cyano-5-pyrimidinyl group.

Examples of aspects of the intermediate for the present compound includethe following compounds:

A compound in which R¹ is a C1-C3 alkyl group or a C2-C5 alkoxyalkylgroup, R² is a hydrogen atom or a C1-C3 alkyl group, and R³ is ahydrogen atom, a halogen atom or a C1-C3 alkyl group in the formula(II).

A compound in which R¹ and R² are bound to each other at an end to be aC3-C4 alkylene group, and R³ is a hydrogen atom, a halogen atom or aC1-C3 alkyl group in the formula (II).

A compound in which R¹ is a C1-C3 alkyl group, R² is a hydrogen atom ora C1-C3 alkyl group, and R³ is a hydrogen atom or a C1-C3 alkyl group inthe formula (II).

A compound in which R¹ is a C1-C3 alkyl group, R² is a hydrogen atom ora C1-C3 alkyl group, and R³ is a halogen atom in the formula (II).

A compound in which R¹ is a C1-C3 alkyl group, R² is a hydrogen atom ora C1-C3 alkyl group, and R³ is a fluorine atom in the formula (II).

A compound in which R¹ is a C1-C3 alkyl group, R² is a C1-C3 alkylgroup, and R³ is a fluorine atom in the formula (II).

A compound in which R¹ is a C1-C3 alkyl group, R² is a methyl group, andR³ is a fluorine atom in the formula (II).

A compound in which R¹ is a C1-C3 alkyl group or a C2-C5 alkoxyalkylgroup, R² is a hydrogen atom or a C1-C3 alkyl group, and R³ is ahydrogen atom, a halogen atom or a C1-C3 alkyl group in the formula(XIII).

A compound in which R¹ and R² are bound to each other at an end to be aC3-C4 alkylene group, and R³ is a hydrogen atom, a halogen atom or aC1-C3 alkyl group in the formula (XIII).

A compound in which R¹ is a C1-C3 alkyl group, R² is a hydrogen atom ora C1-C3 alkyl group, and R³ is a hydrogen atom or a C1-C3 alkyl group inthe formula (XIII).

A compound in which R¹ is a C1-C3 alkyl group, R² is a hydrogen atom ora C1-C3 alkyl group, and R³ is a halogen atom in the formula (XIII).

A compound in which R¹ is a C1-C3 alkyl group, R² is a hydrogen atom ora C1-C3 alkyl group, and R³ is a fluorine atom in the formula (XIII).

A compound in which R¹ is a C1-C3 alkyl group, R² is a C1-C3 alkylgroup, and R³ is a fluorine atom in the formula (XIII).

A compound in which R¹ is a C1-C3 alkyl group, R² is a methyl group, andR³ is a halogen atom in the formula (XIII).

A compound in which R¹ is a C1-C3 alkyl group, R² is a methyl group, andR³ is a fluorine atom in the formula (XIII).

EXAMPLES

The present invention will be explained in more detail by PreparationExamples, Formulation Examples and Test Examples, but the presentinvention is not limited to these Examples.

First, Preparation Examples of the present compound, and PreparationExamples of intermediate for preparing the present compound will beshown by Preparation Examples and Reference Preparation Examples.

Preparation Example 1

211 mg of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate and 95 mgof aminopyrazine were added to 6 ml of bromobenzene, and the mixture wasstirred for 3 hours under the heat-refluxing condition. The reactionmixture was cooled to room temperature, and t-butyl methyl ether wasadded to the mixture. The resulting solid was collected by filtration,washed with t-butyl methyl ether, and dried to obtain 258 mg ofN-(2-pyrazinyl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 1) represented by theformula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.40 (3H, s), 3.54 (3H, s), 6.00 (1H, s),8.34 (2H, m), 9.52 (1H, s), 12.93 (1H, s), 14.67 (1H, s)

Preparation Example 2

Using 2-aminopyrimidine in place of aminopyrazine and according to thesame manner as that of Preparation Example 1,N-(2-pyrimidinyl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 2) represented by theformula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.45 (3H, s), 3.50 (3H, s), 6.26 (1H, s),7.13 (2H, m), 7.48 (2H, m), 12.19 (1H, s), 13.32 (1H, s), 14.28 (1H, s)

Preparation Example 3

Using 4-aminopyrimidine in place of aminopyrazine and according to thesame manner as that of Preparation Example 1,N-(4-pyrimidinyl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 3) represented by theformula:

was obtained.

Preparation Example 4

Using a carboxylic acid ester compound represented by the followingformula:

in place of ethyl 1,6-dimethyl-4-hydroxy-2-oxo-3-pyridinecarboxylate andaccording to the same manner as that of Preparation Example 1, acarboxamide compound (hereinafter, referred to as present compound 4)represented by the formula:

was obtained.

Preparation Example 5

Using methyl4-hydroxy-2-oxo-1,5,6-trimethyl-1,2-dihydropyridine-3-carboxylate inplace of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate andaccording to the same manner as that of Preparation Example 1,N-(2-pyrazinyl)-4-hydroxy-1,5,6-trimethyl-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 5) represented by thefollowing formula:

was obtained.

Preparation Example 6

Using methyl 4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylatein place of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate andaccording to the same manner as that of Preparation Example 1,N-(2-pyrazinyl)-1-methyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 6) represented by theformula:

was obtained.

¹H-NMR (CDCl₃,TMS) δ (ppm): 3.50 (3H, s), 6.25 (1H, d, J=8 Hz), 8.01(1H, d, J=8 Hz), 8.46 (2H, m), 9.39 (1H, s), 13.02 (1H, s), 14.50 (1H,s)

Preparation Example 7

Using 3-amino-1,2,4-triazine in place of aminopyrazine and according tothe same manner as that of Preparation Example 1,N-(1,2,4-triazin-3-yl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 7) represented by theformula:

was obtained.

¹H-NMR (CDCl₃,TMS) δ (ppm): 2.42 (3H, s), 3.55 (3H, s), 6.02 (1H, s),8.58 (1H, d, J=2 Hz), 9.05 (1H, d, J=2 Hz), 13.66 (1H, s), 14.48 (1H, s)

Preparation Example 8

Using 2-amino-1,3,5-triazine in place of aminopyrazine and according tothe same manner as that of Preparation Example 1,N-(1,3,5-triazin-2-yl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 8) represented by theformula:

was obtained.

¹H-NMR (CDCl₃,TMS) δ (ppm): 2.42 (3H, s), 3.54 (3H, s), 6.03 (1H, s),9.04 (2H, s), 13.48 (1H, s), 14.31 (1H, s)

Preparation Example 9

Using 2-amino-6-chloropyrazine in place of aminopyrazine and accordingto the same manner as that of Preparation Example 1,N-(6-chloro-2-pyrazinyl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 9) represented by theformula:

was obtained.

¹H-NMR (CDCl₃,TMS) δ (ppm): 2.41 (3H, s), 3.53 (3H, s), 6.01 (1H, s),8.34 (1H, s), 9.45 (1H, s), 12.99 (1H, s), 14.44 (1H, s)

Preparation Example 10

Using 4-amino-6-methoxypyrimidine in place of aminopyrazine andaccording to the same manner as that of Preparation Example 1,N-(6-methoxy-4-pyrimidinyl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 10) represented by theformula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.39 (3H, s), 3.52 (3H, s), 3.99 (3H, s),5.98 (1H, s), 7.57 (1H, s), 8.54 (1H, s), 12.86 (1H, s), 14.57 (1H, s)

Preparation Example 11

Using 2-amino-5-chloropyrimidine in place of aminopyrazine and accordingto the same manner as that of Preparation Example 1,N-(5-chloro-2-pyrimidinyl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 11) represented by theformula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.40 (3H, s), 3.53 (3H, s) 6.00 (1H, s),8.61 (2H, s), 13.33 (1H, s), 14.67 (1H, s)

Preparation Example 12

Using 3-amino-6-chloropyridazine in place of aminopyrazine and accordingto the same manner as that of Preparation Example 1,N-(6-chloro-3-pyridazinyl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 12) represented by theformula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.41 (3H, s), 3.54 (3H, s), 6.00 (1H, s),7.49 (1H, d, J=9 Hz), 8.50 (1H, d, J=9 Hz), 13.34 (1H, s), 14.40 (1H, s)

Preparation Example 13

Using 2-amino-4-methylpyrimidine in place of aminopyrazine and accordingto the same manner as that of Preparation Example 1,N-(4-methyl-2-pyrimidinyl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 13) represented by theformula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.39 (3H, s), 2.51 (3H, s), 3.53 (3H, s),5.99 (1H, s), 6.91 (1H, d, J=5 Hz), 8.54 (1H, d, J=5 Hz), 13.10 (1H, s),14.92 (1H, s)

Preparation Example 14

Using ethyl1,5-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate in placeof ethyl 1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylateand according to the same manner as that of Preparation Example 1,N-(2-pyrazinyl)-1,5-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 14) represented by theformula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.06 (3H, s), 3.54 (3H, s), 7.24 (1H, s),8.34 (2H, m), 9.52 (1H, d, J=2 Hz), 13.07 (1H, s), 14.37 (1H, s)

Preparation Example 15

Using 2-aminoquinoxaline in place of aminopyrazine and according to thesame manner as that of Preparation Example 1,N-(quinoxalin-2-yl)-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 15) represented by theformula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.42 (3H, s), 3.57 (3H, s), 6.03 (1H, s),7.66 (1H, dd, J=6, 8 Hz), 7.72 (1H, dd, J=6, 8 Hz), 7.95 (1H, d, J=8Hz), 8.08 (1H, d, J=8 Hz), 9.83 (1H, s), 13.17 (1H, s), 14.69 (1H, s)

Preparation Example 16

161 mg of ethyl5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylateand 78 mg of 2-amino-5-chloropyrimidine were added to 1.5 ml ofbromobenzene, and the mixture was stirred for 4 hours under heatrefluxing condition. The reaction mixture was cooled to room temperatureand N-hexane was added to the reaction mixture.

The resulting solid was collected by filtration, washed with a mixtureof t-butyl methyl ether and n-hexane, and dried to obtain 152 mg ofN-(5-chloro-2-pyrimidinyl)-5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 16) represented by theformula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.62 (3H, s), 3.63 (3H, s), 8.63 (2H, s),13.33 (1H, s), 15.72 (1H, s)

Preparation Example 17

168 mg of ethyl5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylateand 82 mg of 3-amino-6-chloropyridazine were added to 1.5 ml ofbromobenzene, and the mixture was stirred for 4 hours under heatrefluxing. The reaction mixture was cooled to room temperature, andn-hexane was added to the reaction mixture. The resulting solid wascollected by filtration, washed with a mixture of t-butyl methyl etherand n-hexane, and dried to obtain 180 mg ofN-(6-chloro-3-pyridazinyl)-5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereafter, referred to as present compound 17) represented by theformula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.63 (3H, s), 3.64 (3H, s) 7.51 (1H, d, J=9Hz), 8.50 (1H, d, J=9 Hz), 13.35 (1H, s), 15.42 (1H, s)

Preparation Example 18

Using methyl 4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylatein place of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate, andusing 2-amino-5-chloropyrimidine in place of aminopyrazine and accordingto the same manner as that of Preparation Example 1,N-(5-chloro-2-pyrimidinyl)-1-methyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 18) represented by thefollowing formula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.56 (3H, s), 6.13 (1H, d, J=7 Hz), 7.39(1H, d, J=7 Hz), 8.62 (2H, s), 13.28 (1H, s), 14.84 (1H, s)

Preparation Example 19

600 mg of ethyl5-fluoro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylateand 194 mg of 3-amino-6-chloropyridazine were added to 5 ml ofbromobenzene, and the mixture was stirred at 160° C. for 4 hours. Thereaction mixture was cooled to room temperature, and subjected to silicagel chromatography (chloroform:methanol=20:1). The resulting crudeproduct was washed with a mixture of t-butyl methyl ether and n-hexane,and dried to obtain 311 mg ofN-(6-chloro-3-pyridazinyl)-5-fluoro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 19) represented by theformula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.45 (3H, d, J=3 Hz), 3.56 (3H, s), 7.51(1H, dd, J=9, 1 Hz), 8.50 (1H, d, J=9 Hz), 13.34 (1H, s), 14.92 (1H, s)

Preparation Example 20

300 mg of5-fluoro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylicacid and 266 mg of carbonyldiimidazole were added to 5 ml ofacetonitrile. The mixture was stirred for 1 hour under heat refluxingcondition. Thereafter, 212 mg of 3-amino-6-chloropyridazine was added tothe mixture, and this was further stirred for 1 hour under heatrefluxing condition. The reaction mixture was cooled to room temperatureand crystals were produced. The crystals were collected by filtration toobtain 250 mg ofN-(6-chloro-3-pyridazinyl)-5-fluoro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(present compound 19):

Preparation Example 21

Using 3-amino-6-methoxypyridazine in place of 3-amino-6-chloropyridazineand according to the same manner as that of Preparation Example 20,N-(6-methoxy-3-pyridazinyl)-1,6-dimethyl-5-fluoro-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter referred to as present compound 20) represented by theformula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.42 (3H, s), 3.55 (3H, s), 4.12 (3H, s),7.01 (1H, d, J=8 Hz), 8.37 (1H, d, J=8 Hz), 13.02 (1H, s), 15.36 (1H,br)

Preparation Example 22

Using 3-amino-6-methylpyridazine in place of 3-amino-6-chloropyridazineand according to the same manner as that of Preparation Example 20,N-(6-methyl-3-pyridazinyl)-1,6-dimethyl-5-fluoro-4-hydroxy-2-oxo-1,2-dihydropyrizine-3-carboxamide(hereinafter, referred to as present compound 21) represented by theformula:

was obtained.

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.44 (3H, s), 2.60 (3H, s), 3.50 (3H, s),7.65 (1H, d, J=9 Hz), 8.27 (1H, d, J=9 Hz), 13.23 (1H, s)

Preparation Example 23

Using 3-amino-6-bromopyridazine in place of 3-amino-6-chloropyridazineand according to the same manner as that of Preparation Example 20,N-(6-bromo-3-pyridazinyl)-1,6-dimethyl-5-fluoro-4-hydroxy-2-oxo-1,2-dihydropyrizine-3-carboxamide(hereinafter, referred to as present compound 22) represented by theformula:

was obtained.

¹H-NMR (DMSO-d₆,TMS) δ (ppm): 2.45 (3H, s), 3.52 (3H, s), 7.25 (1H, s),8.11 (1H, br), 8.48 (1H, br), 13.64 (1H, br)

Preparation Example 24

Using 3-amino-6-cyanopyridazine in place of 3-amino-6-chloropyridazineand according to the same manner as that of Preparation Example 20,N-(6-cyano-3-pyridazinyl)-1,6-dimethyl-5-fluoro-4-hydroxy-2-oxo-1,2-dihydropyrizine-3-carboxamide(hereinafter, referred to as present compound 23) represented by theformula:

was obtained.

¹H-NMR (DMSO-d₆, TMS) δ (ppm): 2.46 (3H, s), 3.52 (3H, s) 8.37 (1H, d,J=9 Hz), 8.54 (1H, d, J=9 Hz), 13.73 (1H, brs)

Preparation Example 25

Using 3-amino-6-methylthiopyridazine in place of3-amino-6-chloropyridazine and according to the same manner as that ofPreparation Example 20,N-(6-methylthio-3-pyridazinyl)-1,6-dimethyl-5-fluoro-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 24) represented by theformula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.44 (3H, s), 2.71 (3H, s), 3.55 (3H, s),7.35 (1H, d, J=9 Hz), 8.28 (1H, d, J=9 Hz), 13.13 (1H, s), 15.21 (1H, s)

Preparation Example 26

Using 3-amino-6-(methoxycarbonylmethylthio)pyridazine in place of3-amino-6-chloropyridazine and according to the same manner as that ofPreparation Example 20,N-(6-methoxycarbonylmethylthio-3-pyridazinyl)-1,6-dimethyl-5-fluoro-4-hydroxy-2-oxo-1,2-dihydropyrizine-3-carboxamide(hereinafter, referred to as present compound 25) represented by theformula:

was obtained.

¹H-NMR (DMSO-d₆, TMS) δ:2.44 (3H, s), 3.50 (3H, s), 3.66 (3H, s), 4.18(2H, s), 7.77 (1H, d, J=9 Hz), 8.24 (1H, d, J=9 Hz), 13.24 (1H, brs),14.80 (1H, brs)

Preparation Example 27

Using 2-amino-5-bromopyrimidine in place of 3-amino-6-chloropyridazineand according to the same manner as that of Preparation Example 20,N-(5-bromo-2-pyrimidinyl)-1,6-dimethyl-5-fluoro-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxamide(hereinafter, referred to as present compound 26) represented by theformula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.46 (3H, s), 3.53 (3H, s), 9.00 (2H, s),13.38 (1H, s), 15.39 (1H, s)

Then, Reference Preparation Examples for preparating intermediates ofthe present compound will be described.

Reference Preparation Example 1

At room temperature, to a mixture of 5.0 g of maleic anhydride and 20 mlof benzene was added 7.9 ml of trimethylsilylazide. The mixture wasstirred at 50 to 60° C. for 3 hours. After the reaction mixture wascooled to room temperature, 4.5 ml of ethanol was added, followed byfurther stirring for 3 hours. The resulting solid was collected byfiltration, and washed with diethyl ether to obtain 300 mg of2H-1,3-oxazine-2,6(3H)-dione represented by the formula:

¹H-NMR (CD₃SOCD₃, TMS) δ (ppm): 5.62 (1H, d, J=8 Hz), 7.66 (1H, d, J=8Hz), 11.55 (1H, s)

Reference Preparation Example 2

At room temperature, to a mixture of 44.8 g of citraconic anhydride and60 ml of chloroform was added 50.0 g of trimethylsilylazide. The mixturewas stirred at 50 to 60° C. for 5 hours. After the reaction mixture wascooled with an ice, 25.0 g of ethanol was added, followed by furtherstirring for 30 minutes. The resulting solid was collected byfiltration, and washed with a mixed solvent of chloroform and ethanol toobtain crude 4-methyl-2H-1,3-oxazine-2,6-(3H)-dione represented by theformula:

Separately, the washing solution was concentrated under reducedpressure. To the residue was added t-butyl methyl ether, followed byfiltration. The resulting solid was washed with t-butyl methyl ether.The filtrate and the washing solution were combined and concentratedunder reduced pressure to obtain crude5-methyl-2H-1,3-oxazine-2,6(3H)-dione represented by the formula:

4-Methyl-2H-1,3-oxazine-2,6(3H)-dione

¹H-NMR (CD₃SOCD₃,TMS) δ (ppm): 2.06 (3H, s), 5.50 (1H, s), 11.47 (1H,s-br)

5-Methyl-2H-1,3-oxazine-2,6(3H)-dione

¹H-NMR (CD₃SOCD₃, TMS) δ (ppm): 1.78 (3H, s), 7.48 (1H, s), 11.47 (1H,s-br)

Reference Preparation Example 3

At room temperature, 1.50 g of 2H-1,3-oxazine-2,6(3H)-dione, 2.19 g ofpotassium carbonate and 3.77 g of methyl iodide were sequentially addedto 30 ml of acetone, and the mixture was stirred for 10 hours under heatrefluxing condition. The reaction mixture was cooled to room temperatureand filtered. The filtrate was concentrated under reduced pressure, andthe resulting solid was dried to obtain 1.46 g of3-methyl-2H-1,3-oxazine-2,6(3H)-dione represented by the formula:

¹H-NMR (CD₃SOCD₃, TMS) δ (ppm): 3.26 (3H, s), 5.68 (1H, d, J=8 Hz), 7.82(1H, d, J=8 Hz)

Reference Preparation Example 4

Using crude 4-methyl-2H-1,3-oxazine-2,6-(3H)-dione in place of2H-1,3-oxazine-2,6(3H)-dione and according to the same manner as that ofReference Preparation Example 3, crude3,4-dimethyl-2H-1,3-oxazine-2,6-(3H) dione represented by the formula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.27 (3H, d), 3.41 (3H, s), 5.49 (1H, d)

Reference Preparation Example 5

Using ethyl bromide in place of methyl iodide and according to the samemanner as that of Reference Preparation Example3,3-ethyl-2H-1,3-oxazine-2,6(3H)-dione represented by formula:

was obtained.

Reference Preparation Example 6

Using chloromethyl ethyl ether in place of methyl iodide and accordingto the same manner as that of Reference Preparation Example3,3-ethoxymethyl-2H-1,3-oxazine-2,6(3H)-dione represented by theformula:

was obtained.

Reference Preparation Example 7

Using crude 5-methyl-2H-1,3-oxazine-2,6(3H)-dione in place of2H-1,3-oxazine-2,6(3H)-dione and according to the same manner as that ofReference Preparation Example 3, crude3,5-dimethyl-2H-1,3-oxazine-2,6(3H)-dione represented by the formula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.94 (3H, d), 3.37 (3H, s), 6.99 (1H,q-like)

Reference Preparation Example 8

Using 4,5-dimethyl-2H-1,3-oxazine-2,6(3H)-dione represented by theformula:

in place of 2H-1,3-oxazine-2,6(3H)-dione and according to the samemanner as that of Reference Preparation Example 3,3,4,5-trimethyl-2H-1,3-oxazine-2,6(3H)-dione represented by the formula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.97 (3H, s), 2.26 (3H, s) 3.42 (3H, s)

Reference Preparation Example 9

Under ice cooling, 568 mg of sodium hydride (60%) was added to a mixtureof 181 mg of dimethyl malonate and 70 ml of N,N-dimethylformamide, andthe mixture was stirred for 20 minutes. After the mixture was heated to80° C., 1.50 g of 3-methyl-2H-1,3-oxazine-2,6(3H)-dione was added to themixture, followed by further stirring at 120° C. for 7 hours. Thereaction mixture was concentrated under reduced pressure, 2 mol/Lhydrochloric acid was added to the residue, and the mixture was stirredat 60° C. for 15 minutes. The mixture was extracted with ethyl acetate.The organic layer was washed with an aqueous saturated sodium chloridesolution, dried with sodium sulfate, filtered, and concentrated. Theresidue was subjected to silica gel column chromatography (eluent: ethylacetate) to obtain 100 mg of methyl4-hydroxy-1-methyl-2-oxo-1,2-dihydropyridine-3-carboxylate representedby the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 3.44 (3H, s), 3.97 (3H, s), 5.97 (1H, d,J=8 Hz), 7.37 (1H, d, J=8 Hz), 13.21 (1H, s)

Reference Preparation Example 10

At room temperature, 1 ml of a solution of 0.71 g of diethyl malonate intetrahydrofuran was added to a mixture of 0.19 g of sodium hydride and 4ml of tetrahydrofuran, and the mixture was stirred for 20 minutes. Atroom temperature, 3 ml of a solution of 0.59 g of3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione in tetrahydrofuran was addedto the mixture, followed by stirring for 2 hours under heat refluxingcondition. The reaction mixture was concentrated under reduced pressure.To the residue were added 10 ml of water and 12 ml of 2 mol/Lhydrochloric acid, followed by extraction with ethyl acetate. Theorganic layer was dried with magnesium sulfate, filtered andconcentrated to obtain 0.57 g of ethyl1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylaterepresented by the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.44 (3H, t, J=7 Hz), 2.34 (3H, s), 3.45(3H, s), 4.43 (2H, q, J=7 Hz), 5.86 (1H, s), 13.26 (1H, s)

Reference Preparation Example 11

Using 3-ethyl-2H-1,3-oxazine-2,6(3H)-dione in place of3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione, and using dimethyl malonatein place of diethyl malonate, and according to the same manner as thatof Reference Preparation Example 10, methyl1-ethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylate represented bythe formula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.33 (3H, t, J=7 Hz), 3.94 (2H, q, J=7 Hz),3.98 (3H, s), 5.98 (1H, d, J=8 Hz), 7.37 (1H, d, J=8 Hz), 13.25 (1H, s)

Reference Preparation Example 12

Using 3-ethoxymethyl-2H-1,3-oxazine-2,6(3H)-dione in place of3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione and according to the samemanner as that of Reference Preparation Example 10, ethyl1-ethoxymethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylaterepresented by the formula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.20 (3H, t, J=7 Hz), 1.44 (3H, t, J=7 Hz),3.60 (2H, q, J=7 Hz), 4.45 (2H, q, J=7 Hz), 5.30 (2H, s), 6.03 (1H, d,J=8 Hz), 7.50 (1H, d, J=8 Hz), 13.55 (1H, s)

Reference Preparation Example 13

Using 3,5-dimethyl-2H-1,3-oxazine-2,6(3H)-dione in place of3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione and according to the samemanner as that of Reference Preparation Example 10, ethyl1,5-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylaterepresented by the formula:

was obtained.

Reference Preparation Example 14

Using 3,4,5-trimethyl-2H-1,3-oxazine-2,6(3H)-dione in place of3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione, and using dimethyl malonatein place of diethyl malonate, and according to the same manner as thatof Reference Preparation Example 10, methyl4-hydroxy-2-oxo-1,5,6-trimethyl-1,2-dihydropyridine-3-carboxylaterepresented by the formula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.05 (3H, s), 2.36 (3H, s), 3.51 (3H, s),3.96 (3H, s), 13.83 (1H, s)

Reference Preparation Example 15

A mixture of 10.1 ml of 2-methyl-1-pyrroline and 2.27 ml of triethylmethanetricarboxylate was stirred at 200° C. for 20 hours. The reactionmixture was cooled to room temperature, and subjected to silica gelcolumn chromatography to obtain 400 mg of carboxylic acid esterrepresented by the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.43 (3H, t, J=7 Hz), 2.14 (2H, m), 3.06(2H, t, J=7 Hz), 4.08 (2H, t, J=7 Hz), 4.41 (2H, q, J=7 Hz), 5.90 (1H,s), 13.35 (1H, s)

Reference Preparation Example 16

After 16.5 g of ethyl 2-chloroacetoacetate and 8.91 g of ethyl carbamatewere sequentially added to 83.9 g of phosphorus oxychloride, the mixturewas stirred at 90° C. for 5 hours. The reaction mixture was concentratedunder reduced pressure, and toluene and water were added to the residue,followed by separation of the layers. The organic layer was extractedwith water four times. The aqueous layers were collected, and extractedwith ethyl acetate four times. The organic layers were collected, washedwith water, dried with magnesium sulfate, filtered and concentrated. Theresulting solid was washed with a mixture of t-butyl methyl ether andn-hexane and dried to obtain5-chloro-4-methyl-2H-1,3-oxazine-2,6(3H)-dione represented by theformula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.34 (3H, s)

Reference Preparation Example 17

At room temperature, 2.11 g of5-chloro-4-methyl-2H-1,3-oxazine-2,6(3H)-dione, 2.07 g of potassiumcarbonate and 1.3 ml of methyl iodide were sequentially added to 40 mlof acetone, and the mixture was stirred for 3 hours under heat refluxingcondition. To the reaction mixture was added 0.5 ml of methyl iodide,and the mixture was further stirred for 2 hours under heat refluxingcondition. The reaction mixture was cooled to room temperature andfiltered. The filtrate was concentrated under reduced pressure. Theresulting solid was dried to obtain 1.74 g of5-chloro-3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione represented by theformula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.48 (3H, s), 3.48 (3H, s)

Reference Preparation Example 18

To 0.43 g of sodium hydride (60%) was added 35 ml of tetrahydrofuran,2.5 ml of a solution of 1.76 g of diethyl malonate in tetrahydrofuranwas added under ice cooling, and the mixture was stirred at roomtemperature for 1 hour. To the mixture was added 1.74 g of5-chrolo-3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione, followed by stirringfor 3.5 hours under heat refluxing condition. The reaction mixture wasconcentrated under reduced pressure. To the residue were sequentiallyadded 20 ml of water and 15 ml of 1 mol/L hydrochloric acid, and thereaction was extracted with 85 ml of chloroform twice. The organic layerwas dried with magnesium sulfate, filtered, and concentrated. Theresidue was washed with n-hexane to obtain 1.52 g of ethyl5-chloro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydroropyridine-3-carboxylaterepresented by the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.45 (3H, t, J=7 Hz), 2.57 (3H, s), 3.54(3H, s), 4.46 (2H, q, J=7 Hz), 14.10 (1H, s)

Reference Preparation Example 19

Using ethyl 2-fluoroacetoacetate in place of ethyl 2-chloroacetoacetateand according to the same manner as that of Reference PreparationExample 16, 5-fluoro-4-methyl-2H-1,3-oxazine-2,6(3H)-dione representedby the formula:

was obtained.

Reference Preparation Example 20

Using 5-fluoro-4-methyl-2H-1,3-oxazine-2,6(3H)-dione in place of5-chloro-4-methyl-2H-1,3-oxazine-2,6(3H)-dione and according to the samemanner as that of Reference Preparation Example 17,5-fluoro-3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione represented by theformula:

was obtained.

Reference Preparation Example 21

Using 5-fluoro-3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione in place of5-chloro-3,4-dimethyl-2H-1,3-oxazine-2,6(3H)-dione and according to thesame manner as that of Reference Preparation Example 18, ethyl5-fluoro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylaterepresented by the formula:

was obtained.

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.45 (3H, d, J=7 Hz), 2.38 (3H, s), 3.46(3H, s), 4.46 (2H, q, J=7 Hz), 13.67 (1H, s), 13.64 (1H, s)

Reference Preparation Example 22

14.4 g of a compound represented by the formula (XVII):

and 6.8 g of diketene were dissolved in 150 ml of acetonitrile, and 1.01g of triethylamine was added thereto at room temperature. The mixturewas stirred at room temperature for 1 hour. Then, 15.5 g of a 40%solution of methylamine in methanol was added to the mixture, followedby stirring at room temperature for 1 hour. Thereafter, the reactionmixture was cooled with an ice, and 30 ml of concentrated hydrochloricacid was added. The resulting crystals were collected by filtration anddried to obtain 17.6 g of2,2-dimethyl-5-(1-hydroxy-3-methylamino-2-butenylidene)-1,3-dioxane-4,6-dionerepresented by the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.70 (6H, s), 2.16 (3H, s), 3.09 (3H, d,J=4 Hz), 6.45 (1H, s), 8.82 (1H, br)

Reference Preparation Example 23

1.0 g of2,2-dimethyl-5-(1-hydroxy-3-methylamino-2-butenylidene)-1,3-dioxane-4,6-dionewas suspended in 20 ml of acetonitrile, 806 mg ofN,N′-difluoro-2,2′-bipyridinium bis(tetrafluoroborate) was addedthereto, and this was stirred at room temperature for 4 hours and at 50°C. for 30 minutes. The reaction mixture was added to 100 ml of icewater, and this was extracted with 100 ml of chloroform twice. Theorganic layer was dried with anhydrous magnesium sulfate andconcentrated, and the residue was subjected to silica gel columnchromatography (eluent: ethyl acetate) to obtain 480 mg of5-fluoro-1,6-dimethyl-4-hydroxy-2-oxo-1,2-dihydropyridine-3-carboxylicacid represented by the formula:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.47 (3H, s), 3.58 (3H, s), 13.89 (1H, br),15.46 (1H, br)

Then, Formulation Examples will be shown. Part represents part byweight, and the present compound is indicated by a compound numberdescribed in Table 1 to Table 3.

Formulation Example 1

Fifty parts of each of the present compounds 1 to 26, 3 parts of calciumligninsulfonate, 2 parts of sodium laurylsulfate, and 45 parts ofsynthetic hydrous silicon oxide are ground and mixed well to obtain eachwettable powder.

Formulation Example 2

Twenty parts of each of the present compounds 1 to 26, and 1.5 parts ofsorbitan trioleate are mixed with 28.5 parts of an aqueous solutioncontaining 2 parts of polyvinyl alcohol, and finely-divided by a wetgrinding method, 40 parts of an aqueous solution containing 0.05 part ofxanthan gum and 0.1 part of aluminum magnesium silicate is added, 10parts of propylene glycol is added and this is stirred and mixed toobtain each flowable preparation.

Formulation Example 3

Two parts of each of the present compounds 1 to 26, 88 parts of kaolinclay and 10 parts of talc are ground and mixed well to obtain each dust.

Formulation Example 4

Five parts of each of the present compounds 1 to 26, 14 parts ofpolyoxyethylene styryl phenyl ether, 6 parts of calciumdodecylbenzenesulfonate and 75 parts of xylene are mixed well to obtaineach emulsifiable concentrate.

Formulation Example 5

Two parts of each of the present compounds 1 to 26, 1 part of synthetichydrous silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts ofbentonite and 65 parts of kaolin clay are ground and mixed well, wateris added, and the mixture is kneaded well, granulated and dried toobtain each granule.

Formulation Example 6

Ten parts of each of the present compounds 1 to 26, 35 parts of whitecarbon containing 50 parts of polyoxyethylene alkyl ether sulfateammonium salt and 55 parts of water are mixed, and finely-divided by awet grinding method to obtain each flowable preparation.

Then, Test Examples demonstrate that the present compound is useful asan agricultural and horticultural fungicide. The present compound isindicated by a compound number.

Test Example 1 Cucumber Grey Mold (Botrytis cinerea) Controlling EffectTest Preventive Effect

A plastic pot was charged with a sand loam, and a cucumber (Name ofplant variety: Sagamihanpaku) was seeded, and grown for 10 days in agreenhouse. Each of flowable preparations of the present compounds 1 to5, 7, 11, 12, 16, 18 and 19 which had been obtained according toFormulation Example 6 was diluted with water to a predeterminedconcentration (500 ppm) to prepare a spraying solution. Each sprayingsolution was foliage-sprayed so that the solution was sufficientlyadhered to cucumber leaves. After spraying, the cucumber was air-driedto such an extent that the spraying solution on the leaves was dried,and a PDA medium containing a spore of cucumber grey mold (Botrytiscinerea) was placed on the cucumber leaves. After inoculation, thecucumber was placed under high humidity at 12° C. for 5 days, and thecontrolling effect was investigated. As a result, an area of a lesion ina plant treated with the present compound 1 to 5, 7, 11, 12, 16, 18 or19 was 10% or less an area of a lesion in a non-treated plant.

Test Example 2 Wheat Scab (Fusarium culmorum) Controlling Effect TestPreventive Effect

A plastic pot was charged with a sand loam, and a wheat (Name of plantvariety: shirogane komugi) was seeded, and was grown for 8 days in agreenhouse. Each of flowable preparations of the present compounds 4, 6,8, 11 and 14 which had been obtained according to Formulation Example 6was diluted with water to a predetermined concentration (500 ppm) toprepare a spraying solution. Each spraying solution was foliage-sprayedso that the solution was sufficiently adhered to wheat leaves. Afterspraying, the wheat was air-dried to such an extent that the sprayingsolution on the leaves was dried, and a spore suspension of wheat scab(Fusarium culmorum) (containing about 2000000 spores per 1 ml ofsuspension) was spraying-inoculated (ratio of about 2 ml per one plant).After spraying, the wheat was placed under high humidity at 23° C. for 4days, and was further placed in a greenhouse 23° C. for 3 days.

Thereafter, the controlling effect was investigated. As a result, anarea of a lesion in a plant treated with the present compound 4, 6, 8,11 or 14 was 10% or less an area of a lesion in a non-treated plant.

INDUSTRIAL APPLICABILITY

By using the present compound, plant diseases can be controlled.

1. A carboxamide compound represented by the formula (I):

[wherein Q represents a nitrogen-containing 6-membered aromaticheterocyclic group optionally fused with a benzene ring, two or more ofring constitutional atoms of the heterocyclic group are nitrogen atoms,the heterocyclic group may be substituted with at least one groupselected from the group consisting of a C1-C3 alkyl group, a C1-C3haloalkyl group, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group anda nitro group, R¹ represents a C1-C3 alkyl group or a C2-C5 alkoxyalkylgroup, R² represents a hydrogen atom or a C1-C3 alkyl group, or R¹ andR² are bound to each other at an end to represent a C3-C4 alkylenegroup, R³ represents a hydrogen atom, a halogen atom or a C1-C3 alkylgroup.]
 2. The carboxamide compound according to claim 1, wherein Qrepresents a nitrogen-containing 6-membered aromatic heterocyclic groupoptionally fused with a benzene ring, two or more of ring constitutionalatoms of the heterocyclic group are nitrogen atoms, the heterocyclicgroup may be substituted with at least one group selected from the groupconsisting of a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3alkoxy group, a halogen atom, a cyano group and a nitro group, R¹represents a C1-C3 alkyl group or a C2-C5 alkoxyalkyl group, R²represents a hydrogen atom or a C1-C3 alkyl group, or R¹ and R² arebound to each other at an end to represent a C3-C4 alkylene group. R³represents a hydrogen atom, a halogen atom or a C1-C3 alkyl group.] 3.The carboxamide compound according to claim 1, wherein Q is a 6-memberedaromatic heterocyclic group in which two or more ring constitutionalatoms are nitrogen atoms, and the heterocyclic group may be substitutedwith at least one group selected from the group consisting of a C1-C3alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, a C1-C3alkylthio group, a (C1-C3 alkoxycarbonyl)C1-C3 alkylthio group, ahalogen atom, a cyano group and a nitro group.
 4. The carboxamidecompound according to claim 1, wherein Q is a 6-membered aromaticheterocyclic group in which two or more ring constitutional atoms arenitrogen atoms, and the heterocyclic group may be substituted with atleast one group selected from the group consisting of a C1-C3 alkylgroup, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, a halogen atom, acyano group and a nitro group.
 5. The carboxamide compound according toclaim 1, wherein Q is a heterocyclic group which is a 2-pyrimidinylgroup, a 4-pyrimidinyl group, a 5-pyrimidinyl group, a 2-pyrazinylgroup, a 3-pyridazinyl group, a 4-pyridazinyl group, a1,2,4-triazin-3-yl group, a 1,3,5-triazin-2-yl group, a quinoxalin-2-ylgroup, a quinazolin-2-yl group or a cinnolin-3-yl group, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl) C1-C3 alkylthio group, a halogen atom, a cyano group anda nitro group.
 6. The carboxamide compound according to claim 1, whereinQ is a heterocyclic group which is a 2-pyrimidinyl group, a4-pyrimidinyl group, a 5-pyrimidinyl group, a 2-pyrazinyl group, a3-pyridazinyl group, a 4-pyridazinyl group, a 1,2,4-triazin-3-yl group,a 1,3,5-triazin-2-yl group, a quinoxalin-2-yl group, a quinazolin-2-ylgroup or a cinnolin-3-yl group, and the heterocyclic group may besubstituted with at least one group selected from the group consistingof a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, ahalogen atom, a cyano group and a nitro group.
 7. The carboxamidecompound according to claim 1, wherein Q is a heterocyclic group whichis a 2-pyrimidinyl group, a 4-pyrimidinyl group, a 5-pyrimidinyl group,a 2-pyrazinyl group, a 3-pyridazinyl group, a 4-pyridazinyl group, a1,2,4-triazin-3-yl group or a 1,3,5-triazin-2-yl group, and theheterocyclic group may be substituted with at least one group selectedfrom the group consisting of a C1-C3 alkyl group, a C1-C3 haloalkylgroup, a C1-C3 alkoxy group, a C1-C3 alkylthio group, a (C1-C3alkoxycarbonyl)C1-C3 alkylthio group, a halogen atom, a cyano group anda nitro group.
 8. The carboxamide compound according to claim 1, whereinQ is a heterocyclic group which is a 2-pyrimidinyl group, a4-pyrimidinyl group, a 5-pyrimidinyl group, a 2-pyrazinyl group, a3-pyridazinyl group, a 4-pyridazinyl group, a 1,2,4-triazin-3-yl groupor a 1,3,5-triazin-2-yl group, and the heterocyclic group may besubstituted with at least one group selected from the group consistingof a C1-C3 alkyl group, a C1-C3 haloalkyl group, a C1-C3 alkoxy group, ahalogen atom, a cyano group and a nitro group.
 9. The carboxamidecompound according to claim 1, wherein R³ is a hydrogen atom or a C1-C3alkyl group.
 10. The carboxamide compound according to claim 1, whereinR³ is a hydrogen atom or a halogen atom.
 11. A plant disease controllingagent, comprising a carboxamide compound as defined in claim 1 as anactive ingredient, and an inert carrier.
 12. A method of controlling aplant disease, comprising a step of treating a plant or a soil where aplant grows with an effective amount of the carboxamide compound asdefined in claim
 1. 13. Use of a carboxamide compound as defined inclaim 1, for controlling a plant disease.